Insecticidal compositions containing polyetheramines



Patented July 27, 1943 INSECTICIDAL COMPOSITIONS CONTAIN- ING POLYETHERAMINES William F. Heater, Drexel Hula Pa assignor to Rlihm & Haas Company, Philadelphia, Pa., a

corporation of Delaware No Drawing. Application August 26, 1941, Serial No. 408,329

8 Claims.

This invention relates to insecticidal compositions containing as an active parasiticidal agent a compound of the formula tmocamnmmmt'am wherein R is an aliphatic hydrocarbon group having one to twelve carbon atoms, Cum: represents an alkylene group in which n is an integer having a value of two to four inclusive, is an integer having a value of one or more, m is an integer having a value of 2 to 3 inclusive, and R is hydrogen or a hydrocarbon group or a hydroxyalkyl group. Typical groups for R include branched, straight chain, saturated, and unsaturated groups, such as methyl, ethyl, isopropyl allyl, methallyl, isobutyl, n-butyl, amyl, hexyl, octyl, capryl, undecenyl, dodecyl, etc. In addi tion to hydrogen, R may represent a hydrocarbon group such as methyl, ethyl, allyl, butyl, octyl, phenyl, benzyl, cyclohexyl, etc., or a hydroxyalkyl group, such as C2H4OH or -CH='CH0HCH3.

The group represented by C1|H2n may be an alkylene group such as momma-'- or a branched chain such as -CH2CH(CH3) or --CH2CH(CH3) CH2-.

The open chain polyether amines of this invention may be prepared from alkoxyalkylene halides, the alkylene group of which may be interrupted by oxygen, by reaction with ammonia under pressure. The product may be distilled to separate the secondary and tertiary amines from any primary amine which may be formed. The primary amine may be returned to the reaction system as this type of primary amine is less desirable as an insecticide than the amines containing two or three ether chains. In-place of ammonia there may be used a primary aliphatic, cycloaliphatic, or aryl amine, such as methylamine, ethylamlne, cyclohexylamine, aniline, or the like. In this case the products having two ether-containing radicals are separated and used in insecticidal compositions.

The secondary amines forming part of the reaction products and having one ether substituent and a second substituent corresponding to that of the primary amine used may, if desired, be used in a second reaction mixture and converted to the tertiary amine having two ether-containing substituents. These secondary amines, howand ever, also possess good insecticidal activity and their use in insecticidal compositions is described in application SerialNo. 408,328, filed on even date.

Typical of the compounds which may be thus prepared are the following: assess-as the to human beings or other animals, or to plants; While the alkoxyalkylene amines are useful in aqueous sprays, they are especially eflective when applied from solvents, such as petroleum naphthas. These solutions are useful in destroying flies, fleas, mosquitoes, roaches and the like. The alkoxyalkylene amines are also useful in dormant sprays, which may contain in addition thereto emulsified oils and these sprays are particularly effective for killing the eggs or European red mite, aphis, etc. 1 r

The following examples illustrate the preparation and use of typical alkoxyalkylene amines.

Example 1 A mixture of parts of butoxyethoxyethyl chloride and 34 parts of anhydrous ammonia was heated in an autoclave at 225 C. under pressure for four hours. The reaction mixture was cooled, treated with alkali, and distilled. The fraction boiling between 151 and 156 C. at 2.5 mm. pressure was found to consist essentially of (C4H9OC2H4OC2H4) zNH. The fraction distilling between 180 and 210 C. at 2.5 mm. pressure consisted of (C4H9OC2H4OC1H03N. These fractions were tested according to the standard Peet- Grady procedure as the sole toxicants in fly a knockdown of 97% and a kill after 24 hours of +17 compared with the O. T. I. A mixture of 50% or each the two products was also tested in a 5% spray giving a 97% knockdown and a kill of +16 compared to the 0. T. I. A particularly significant feature 0! all or these sprays was that they had no more odor thanthe kerosene without the toxicants. The sprays caused nonasal or skin irritation to workers exposed to them.

A concentrate was prepared from parts of (ClHtOCrHiOCsHOiN, parts of the reaction product of polyglycerol and cocoanut acids (as an emulsifier), and '75 parts or a petroleum spray oil. This concentrate was diluted at 1:100 with water and applied in March as a dormant spray to apple trees which had been infested with red mites and aphids. At the end 01 April counts were made of the red mite e gs which had hatched and those which had been killed. A control up to 84% was obtained on different apple trees. Control with a known insecticide used for comparison in the same orchard was 60%.

The combination described above was used at 1:100 against eggs of the bean weevil with a 96% kill and against the meal worm with 100% kill. Against the meal worm at 1:200 a 95% kill was obtained.

Another concentrated spray material was prepared from 20 parts of the above compounds,

parts of the same emulsifier, and parts of spray oil. This was applied in aqueous sprays at 1:300 to greenhouse roses infested with red spiders. Controls of 93% and 94% were obtained. No injury resulted to the plants. The same sprays applied to bean plants ini'ested with red spiders consistently gave a 100% control.

Example 2 A mixture of 225 parts of a butoxyethoxyethyl bromide and parts of methylamine was heated in an autoclave at 225-250 C. for about four hours. The reaction product was cooled, treated with alkali, and distilled. The fraction distilling between 140 C. and 150 C. at 3 mm. pressure corresponded in composition to (Cd-1900213340 CsH-i) sNCI-Is pressure. An aqueous spray containing 0.5% of this material gave 100% control of Mexican bean beetle larvae on bean plants and a 73% control at 1 lb. per 100 gallons of spray.

Another similar product was prepared from cyclohexyl amine and butoxyethoxyethyl chloride. The resulting tertiary amine boiled at 125- 150 C. at 2.5 mm. It showed particular efiectiveness against aphids and bean beetle larvae.

Example 3 I Two parts or the mixture oi. 50% each of (C4H0OC2H4OC1HO2NH and (Cd-lsOCamOCsHnaN was combined with three parts of pyrethrum (20:1) extract, diluted with kerosene to parts, and tested asainst flies by the Feet-Grady technique. A knockdown of 97% was obtained and a kill 01 +30 compared to the O. T. I.

One part 0! the mixture of amines and four parts of the Dyrethrum extract in 100 parts or fly spray gave a knockdown of 99% and a kill or +21 compared to the 0. T. L Three parts oi'the amine mixture with three parts 01' pyrethrum extract in 100 parts of fly spray gave a knockdown of 99% and a kill or +30 compared to the O. T. I.

j Ewample 4 The mixture 01' the secondary and tertiary amines shown above was tested against roaches. A 1% solution gave a kill-oi +2 compared to the O. T. I. (5% pyrethrum 20:1) while a 2% solution oi the mixed amines gave a kill 01 +17 and 8% a kill of +28.

Example 5 A mixture of methyl alcohol, chloroethyl ether, sodium hydroxide, and water was heated at 80 C. for 24 hours, cooled, filtered, and fractionated. From the distillates there were taken the ,fractions which contained about the correct chlo- Without further purification these fractions were made into a 5% fly spray and tested by the Feet-Grady procedure. The knockdown obtained with the secondary product was 56% and the kill in 24 hours --12 compared to the 0. T. I. The tertiary amine gave a kill of --9 and a knockdown of 65%. Both fly sprays were free from odor or irritation.

Example 6 To a mixture of 74.6 parts oi. triethanolainine and 60 parts of sodium hydroxide there was added 270 parts of butoxyethoxy ethyl chloride and the mixture was heated for two hours at C.- C. on an oil bath under a reduced pressure of about 60 mm. As water formed in the reaction, it was removed. The reacted mixture, was cooled, washed with water, separated, dried over sodium sulfate and distilled under reduced pressure. The fraction distilling between 225 and 230 C.. under 3 mm. pressure, consisting of 46 parts, corresponded in composition to (C4H9OC2H4OC2H4OC2H4) 2NC2H4OH. It contained by analysis 3.12% of nitrogen.

This fraction was taken up in kerosene to prepare a fiy spray which was adjusted to a 5% concentration of the above product. By the Fest- Grady test this spray gave an 86% knockdown and a kill of -5 against the 0. T. I.

Example 7 with a small amount of the mono-octyloxyethyl ethanolamine. The fraction distilling between 185 C. and 205C. was practically pure bisoctyloxyethyl ethanolamine. These products in a series of tests gave knockdowns of 74 to 77% and kills from 14 to against the 0. T. I.

By methods generally similar to those de- I scribed above, there may be prepared a great variety of aliphatic oxyalkylene amines which are secondary or tertiary. In contrast therein the corresponding primary amines appear to be less effective and are not sufliciently free from odor and irritation. The secondary and tertiary ether amines provide a wide variety of ether amines from which one or more members may be selected for any particular insecticidal or ovicidal purpose. The most available compounds are those containing ethylene ether groups and of these the ether amines having a terminal aliphatic group of 3 to 8 carbon atoms and 2 to 4 oxyethyl groups are preferred. It is also preferred in the case of those tertiary amines having two alkoxyalkylene groups that the third N-substituent have not over seven carbon atoms.

The alkoxyalkylenesecondary and tertiary amines have an unusual balance of desirable properties. They give a high knockdown and a good kill, yet they are practically odorless in sprays and are free from irritating eflects. Compared to non-ether amines, they have an improved knockdown and they are definitely superior in regard to odor and irritation. They have.

formula Hum) slsuNR'J-n whereinnisanaliphatiehydrocarbongroupof lessthanltcsrbonatomacsnarepresentsan alkylene group in which n is an integer having a value of,two to four inclusive, :1: is an integer of at least one, m is an integer having a value of two to three inclusive, and R is a member ofthe class consisting of hydrogen, hydroxyalkyl, and hydrocarbon groups.

2. Insecticidal and ovicidal compositions having as an active ingredient a compound of the formula wherein R is an aliphatic hydrocarbon group of less than 13 carbon atoms, n and a: are integers having values of two to four inclusive, m is an integer having a value of two to three inclusive, and R is a hydrocarbon group of not over seven carbon atoms.

3. Insecticidal and ovicidal compositions having as an active ingredient a compound of the formula formula [R(0CHm) :hNH

wherein R is an alkyl group of three to eight carbon atoms, and n and a: are integers having values of two to four inclusive.

5. Insecticidal and ovicidal compositions having as an active ingredient a compound of the formula wherein R is an alkyl group of three to eight carbon atoms, and n and a: are integers having values of two to four inclusive.

6. An insecticidal and ovicidal composition having as an active ingredient a compound of th formula wherein m is an integer having a value of two to three inclusive.

7. An insecticidal and ovicidal composition having as an active ingredient a compound of the formula (94H9OCH10HQOCH1CH91NH 8. An insecticidal and ovicidal composition having as an active ingredient a compound of the formula 

